CN106496080A - A kind of preparation method of mercapto-functionalized aryl carboxylic acid - Google Patents
A kind of preparation method of mercapto-functionalized aryl carboxylic acid Download PDFInfo
- Publication number
- CN106496080A CN106496080A CN201610913260.7A CN201610913260A CN106496080A CN 106496080 A CN106496080 A CN 106496080A CN 201610913260 A CN201610913260 A CN 201610913260A CN 106496080 A CN106496080 A CN 106496080A
- Authority
- CN
- China
- Prior art keywords
- reaction
- preparation
- acid
- sulfydryl
- mercapto
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
- C07C319/06—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols from sulfides, hydropolysulfides or polysulfides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
Abstract
The invention provides a kind of preparation method of mercapto-functionalized aryl carboxylic acid, comprises the following steps：A) to 2, the carboxyl of 3,5,6 tetrafluoro terephthalic acid (TPA)s is protected, and obtains intermediate 1；B intermediate 1 and sulfydryl acid esters are carried out substitution reaction under conditions of alkali metal salt presence), intermediate 2 is obtained；C) intermediate 2 is hydrolyzed reaction, obtains mercapto-functionalized aryl carboxylic acid., using sulfydryl acid esters as reaction raw materials, cost is relatively low, and toxicity is low for the present invention, almost without smell, safety and environmental protection；And reaction condition is gentle, almost without energy consumption, is swift in response, and energy-conserving and environment-protective provide possibility for industrialized production；The reaction simultaneously has higher conversion ratio and yield.
Description
Technical field
A kind of the present invention relates to compound synthesis technical field, more particularly to preparation side of mercapto-functionalized aryl carboxylic acid
Method.
Background technology
Metal-organic framework materials (Metal-Organic framework, MOF) are obtained as emerging porous material
Fast development, the polyporous materials can by the design to functional ligand, and then orient self assembly go out with preset structure and
The metal-organic framework material of function.
Research based on early stage finds that sulfydryl aromatic carboxylic acids have annexed soft or hard atom and have been integrated (hard and soft acid and base reason
By), used as hard base, the S on sulfydryl makes the advantage of this kind of compound very notable as soft base to the wherein O on carboxyl.Work as selection
Hard acid metalloid ion such as (Zr4+) used as coordination center, central ion can be selected and carboxyl formation metal organic frame, and sulfydryl
It is not involved in being coordinated, dissociates and modify the mercapto-functionalized aryl carboxylic acid compound of framework material.Sulfydryl is incorporated into metallic organic framework
In material, its advantage major embodiment is as follows：1) mercapto functional group is closed after the activity of organic aspect is conducive to MOF materials to carry out
Into modification；2) the strong combination of mercapto functional group and metal ion enable MOF materials absorb a variety of metals from
Son is so as to reaching the purpose of heavy-metal ion removal.
In addition, sulfhydryl compound still synthesize medicine intermediate and important industrial chemicals, mainly have mercaptan and
Two big class of thiophenol.The sulfydryl of sulfhydryl compound is easily quickly complexed with heavy metals such as mercury ion, silver ions, and forms stable coordination
Compound.Therefore, before the compound of thiohydroxy-containing group has huge application in terms of absorption, separate precious metal and heavy metal
Scape.
At present, synthesize the reaction of sulfhydryl compound, condition is harsh and acutely, and yield is not high, cumbersome, raw materials used into
This height, toxicity is big and large-scale production that limit sulfhydryl compound with factors such as ferocious penetrating odors.
Such as Jun He etc. (CN104447452A) report a kind of side of the mercapto-functionalized polyaryl carboxylic acids compound of synthesis
Method, reaction equation such as formula 1：
Relatively acutely (reaction temperature is higher), conversion ratio and yield be not high, and the reaction time is longer for the method reaction condition, and
And the method needed raw material (sodium methyl mercaptide, chloride compounds) price is costly, toxicity is big and there is ferocious stimulation
Property smell, causes very big harm, and is unfavorable for environmental protection and industrialized production to the body of operating personnel.
Content of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of preparation side of mercapto-functionalized aryl carboxylic acid
Method, reaction condition are gentle, and cost of material is low.
The invention provides a kind of preparation method of mercapto-functionalized aryl carboxylic acid, comprises the following steps：
A) to 2, the carboxyl of 3,5,6- tetrafluoro terephthalic acid (TPA)s is protected, and obtains intermediate 1；
B intermediate 1 and sulfydryl acid esters are carried out substitution reaction under conditions of alkali metal salt presence), intermediate 2 is obtained；
C) intermediate 2 is hydrolyzed reaction, obtains mercapto-functionalized aryl carboxylic acid.
Preferably, step A) it is specially：
2,3,5,6- tetrafluoro terephthalic acid (TPA)s under conditions of methyl alcohol with the concentrated sulfuric acid carry out esterification, obtain 2,3,5,
6- tetrafluoro terephthalic acid (TPA) methyl esters.
Preferably, the temperature of the esterification is backflow, and the time is 1～24h.
Preferably, the sulfydryl acid esters is 3- sulfydryl hexanol capronates, methyl thioglycolate, 3- mercaptopropionic acid -3- methoxies
One or more in butyl ester, 2 mercaptopropionic acid propyl ester, 3- mercaptopropionic acid -2- b hexyls.
Preferably, the alkali metal salt be potassium phosphate, sodium carbonate, sodium acetate, cesium carbonate, potassium carbonate, in potassium acetate one
Plant or multiple.
Preferably, the mol ratio of the intermediate 1, sulfydryl acid esters and alkali metal salt is 1：(0.5～10)：(1～20).
Preferably, the solvent of the substitution reaction be tetrahydrofuran, isopropanol, dimethyl sulfoxide, acetonitrile, N, N- dimethyl methyls
One or more in acid amides, 1,3- dimethyl-2-imidazolinones, Macrogol 600, DMAC N,N' dimethyl acetamide.
Preferably, the temperature of the substitution reaction is 0～80 DEG C, and the reaction time is 0.5～12h.
Preferably, the substitution reaction is a substitution reaction, two substitution reactions, three substitution reactions or four substitution reactions.
Preferably, the hydrolysis is carried out under strongly alkaline conditions.
Compared with prior art, the invention provides a kind of preparation method of mercapto-functionalized aryl carboxylic acid, including following
Step：A) to 2, the carboxyl of 3,5,6- tetrafluoro terephthalic acid (TPA)s is protected, and obtains intermediate 1；B) by intermediate 1 and mercaptan acid
Ester carries out substitution reaction under conditions of alkali metal salt presence, obtains intermediate 2；C) intermediate 2 is hydrolyzed reaction, obtains mercapto
Base functionalization aryl carboxylic acid., using sulfydryl acid esters as reaction raw materials, cost is relatively low, and toxicity is low for the present invention, almost not gas
Taste, safety and environmental protection；And reaction condition is gentle, almost without energy consumption, is swift in response, and energy-conserving and environment-protective are provided for industrialized production
May；The reaction simultaneously has higher conversion ratio and yield.
Description of the drawings
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of 1 intermediate 2 of embodiment；
Fig. 2 is the nuclear-magnetism fluorine spectrogram of 1 intermediate 2 of embodiment；
Fig. 3 is the nucleus magnetic hydrogen spectrum figure of 1 product of embodiment；
Fig. 4 is the nuclear-magnetism fluorine spectrogram of 1 product of embodiment；
Fig. 5 is the mass spectrogram of 1 product of embodiment.
Specific embodiment
The invention provides a kind of preparation method of mercapto-functionalized aryl carboxylic acid, comprises the following steps：
A) to 2, the carboxyl of 3,5,6- tetrafluoro terephthalic acid (TPA)s is protected, and obtains intermediate 1；
B intermediate 1 and sulfydryl acid esters are carried out substitution reaction under conditions of alkali metal salt presence), intermediate 2 is obtained；
C) intermediate 2 is hydrolyzed reaction, obtains mercapto-functionalized aryl carboxylic acid.
The present invention first to 2, protected, it is preferred that by 2 by the carboxyl of 3,5,6- tetrafluoro terephthalic acid (TPA)s, and 3,5,6- tetra-
Fluorine terephthalic acid (TPA) under conditions of methyl alcohol with the concentrated sulfuric acid carries out esterification, obtains 2,3,5,6- tetrafluoro terephthalic acid (TPA) first
Ester.
The temperature of the esterification is preferably and flows back, i.e., 50～100 DEG C, and the reaction time is preferably 1～24h.
Specifically, 2,3,5,6- tetrafluoro terephthalic acid (TPA) of raw material, methyl alcohol and the concentrated sulfuric acid are added to reflux condenser
In reactor, stirring is opened, backflow is warmed up to and is prepared within 1～24 hour intermediate 1, i.e., 2,3,5,6- tetrafluoro terephthalic acid (TPA)s
Methyl esters.
After reaction terminates, reaction is post-processed, it is preferred that reaction system is cooled to room temperature, adds a large amount of distilled water,
There are a large amount of solids to separate out, reduce pressure suction filtration, obtains white plates crystal product, as intermediate 1.
Then the intermediate 1 and sulfydryl acid esters of preparation are carried out substitution reaction under conditions of alkali metal salt presence, is obtained
Intermediate 2.
The sulfydryl acid esters is preferably 3- sulfydryl hexanol capronates, methyl thioglycolate, 3- mercaptopropionic acid -3- methoxy fourths
One or more in ester, 2 mercaptopropionic acid propyl ester, 3- mercaptopropionic acid -2- b hexyls, is more preferably one or two.
The alkali metal salt be preferably potassium phosphate, sodium carbonate, sodium acetate, cesium carbonate, potassium carbonate, the one kind in potassium acetate or
Multiple.
The mol ratio of the intermediate 1, sulfydryl acid esters and alkali metal salt is preferably 1：(0.5～10)：(1～20).
The solvent of the substitution reaction is preferably tetrahydrofuran, isopropanol, dimethyl sulfoxide, acetonitrile, N, N- dimethyl formyls
One or more in amine, 1,3- dimethyl-2-imidazolinones, Macrogol 600, DMAC N,N' dimethyl acetamide.
The temperature of the substitution reaction is preferably 0～80 DEG C, and the reaction time is preferably 0.5～12h.
The substitution reaction is preferably carried out in an inert atmosphere.
Specifically, intermediate 1, sulfydryl acid esters and alkali metal salt are added in reactor, then is added organic solvents into anti-
Answer in device, reaction prepares intermediate 2 in 0.5～12 hour at 0～80 DEG C in an inert atmosphere.
After reaction terminates, reaction is post-processed, it is preferred that then reaction system is carried out through organic layer is obtained by extraction
Pillar layer separation, obtains colourless viscous liquid, as intermediate 2.
In the present invention, the substitution reaction can pass through the consumption for controlling sulfydryl acid esters, i.e., by changing intermediate 1 and mercapto
The different proportion of base acid esters, Control release carry out a substitution reaction of replacement fluorine atom (F), two substitution reactions, three substitution reactions
Or four substitution reactions.So that the method is applied to the sulfhydrylation of the aryl compound of halogen atom-containing (such as F atom)
Reaction.
When a substitution reaction is carried out, the intermediate 1 is 1 with the mol ratio of sulfydryl acid esters:(0.1～5)；
When two substitution reactions is carried out, the intermediate 1 is 1 with the mol ratio of sulfydryl acid esters:(0.5～10)；
When three substitution reactions is carried out, the intermediate 1 is 1 with the mol ratio of sulfydryl acid esters:(1～15)；
When four substitution reactions is carried out, the intermediate 1 is 1 with the mol ratio of sulfydryl acid esters:(1～20).
Then intermediate 2 is hydrolyzed reaction, you can obtain mercapto-functionalized aryl carboxylic acid.
Preferably, the hydrolysis is carried out under strongly alkaline conditions.The strong alkaline condition can pass through to add highly basic
Property compound obtain, the present invention to the strongly alkaline compound and is not particularly limited, and can be well known to those skilled in the art
Strongly alkaline compound, the present invention are preferably KOH or NaOH.
The hydrolysis is preferably carried out in the mixed solvent of alcohols solvent and water.The alcohols solvent is preferably second
Alcohol.
The temperature of the hydrolysis is preferably 25～140 DEG C, and the reaction time is preferably 0.5～24h.
After reaction terminates, reaction is post-processed, it is preferred that reaction system is cooled to room temperature, adds excessive concentrated hydrochloric acid,
Solution is adjusted to acidity, after 0.5～2h is stirred at room temperature, a large amount of distilled water is added in system, there are a large amount of yellow solids to separate out, subtract
Pressure suction filtration, obtains product as yellow powder, as mercapto-functionalized aryl carboxylic acid sterling, and its yield is higher than 90%.
The reaction equation of above-mentioned reaction is as follows：
Wherein, Base is alkali metal salt；Solvent represents organic solvent；X=1,2,3 ... .n, it is furthermore preferred that x is 1
～10 integer.
, using sulfydryl acid esters as reaction raw materials, cost is relatively low, and toxicity is low for the present invention, almost without smell, safety collar
Protect；And reaction condition is gentle, almost without energy consumption, is swift in response, and energy-conserving and environment-protective provide possibility for industrialized production；With
When the reaction mercapto-functionalized aryl carboxylic acid with higher conversion ratio and yield, preparation there is higher purity.
In order to further illustrate the present invention, with reference to embodiment to the mercapto-functionalized aryl carboxylic acid for providing of the invention
Preparation method is described in detail.
Embodiment 1
The synthesis step of intermediate 1：
(1) the single port circle that 2,3,5,6- tetrafluoro terephthalic acid (TPA) (1190mg, 5mmol) of raw material adds 100mL to dry is weighed
In the flask of bottom.
(2) measure methyl alcohol (anhydrous, 50mL) with graduated cylinder to be added in single necked round bottom flask.
(3) concentrated sulfuric acid (2mL) is added dropwise, under room temperature, stirs 10min.It is subsequently placed in backflow 24h in oil bath.Question response is complete
Afterwards, room temperature being cooled to, substantial amounts of distilled water being added in mixture, there are a large amount of solids to separate out, reduce pressure suction filtration, obtains white plates
Crystalline product (i.e. intermediate 1) 1237mg, yield 93%, purity 98%.
The synthesis step of intermediate 2：
(1) potassium carbonate (2208mg, 16mmol) is placed in the reaction eggplant bottle of 25mL dryings, under nitrogen protection using note
Emitter throws 3- mercaptopropionic acids -2- Octyl Nitrites (1.9mL, 8.3mmol) in reaction eggplant bottle into.
(2) by the DMF (anhydrous, 15mL) after bubbling 10min under a nitrogen, shifted by vacuum tube
In the reaction eggplant bottle dried to 25mL.
(3) last, under nitrogen protection, intermediate obtained above 1 (1064mg, 4mmol) is added to 25mL dryings
Reaction eggplant bottle in, open stirring 0.5～12h.
(4), after reacting completely, the organic layer that is obtained by extraction, by silica gel chromatography post separation are purified, and obtain colourless viscous liquid product
Thing (i.e. intermediate 2) 1903mg, yield 72%, purity 98%.
The structure of intermediate 2 is detected, as a result see that Fig. 1 and Fig. 2, Fig. 1 are the nucleus magnetic hydrogen spectrum figures of intermediate 2, Fig. 2 is
The nuclear-magnetism fluorine spectrogram of intermediate 2.
As seen from Figure 1, embodiment 1 has carried out two substitution reactions.
The synthesis step of end-product 3：
Intermediate 2 (1800mg, 2.72mmol) is added in the ethanol water of 24mL potassium hydroxide, 90 DEG C of oil is placed in
Flow back in bath 24h.Reaction is finished, and is cooled to room temperature, adds excessive concentrated hydrochloric acid, makes solution in acidity.After 1h is stirred at room temperature, to
Substantial amounts of distilled water is added in mixed solution, there are a large amount of yellow solids to separate out, reduce pressure suction filtration, obtain yellow powder product and (produce eventually
Thing 3) 658mg, yield 91%, purity 97%.
Product structure is detected, testing result is shown in Fig. 3 and Fig. 4, wherein, Fig. 3 is the nucleus magnetic hydrogen spectrum figure of product, Fig. 4
It is the nuclear-magnetism fluorine spectrogram of product.
Can be seen that the displacement that H is not found in nucleus magnetic hydrogen spectrum figure by Fig. 3 and Fig. 4.Reason is on hydroxyl and sulfydryl
Hydrogen is more active, can be easy to be exchanged, can not manifest out on collection of illustrative plates.It can be seen that, the side chain substituents of intermediate 2 are hydrolyzed
Fall.
Molecular structure is detected using mass spectrograph, its mass spectrogram is shown in Fig. 5.
Embodiment 2
The synthesis step of intermediate 1：
(1) single neck round bottom that 2,3,5,6- tetrafluoro terephthalic acid (TPA) (952mg, 4mmol) of raw material adds 80mL to dry is weighed
In flask.
(2) measure methyl alcohol (anhydrous, 30mL) with graduated cylinder to be added in single necked round bottom flask.
(3) concentrated sulfuric acid (1mL) is added dropwise, under room temperature, stirs 10min.It is subsequently placed in backflow 24h in oil bath.Question response is complete
Afterwards, room temperature being cooled to, substantial amounts of distilled water being added in mixture, there are a large amount of solids to separate out, reduce pressure suction filtration, obtains white plates
Crystalline product (i.e. intermediate 1) 968mg, yield 93%, purity 98%.
The synthesis step of intermediate 2：
(1) potassium acetate (1568mg, 16mmol) is placed in the reaction eggplant bottle of 25mL dryings, under nitrogen protection using note
Emitter adds 2 mercaptopropionic acid propyl ester (1228.4mg, 8.3mmol) in reaction eggplant bottle.
(2) by the DMF (anhydrous, 15mL) after bubbling 10min under a nitrogen, shifted by vacuum tube
In the reaction eggplant bottle dried to 25mL.
(3) last, under nitrogen protection, intermediate obtained above 1 (1064mg, 4mmol) is added to 25mL dryings
Reaction eggplant bottle in, open stirring 0.5～12h.
(4), after reacting completely, the organic layer that is obtained by extraction, by silica gel chromatography post separation are purified, and obtain colourless viscous liquid product
Thing (i.e. intermediate 2) 1830mg, yield 69%, purity 97%.
The synthesis step of end-product 3：
Intermediate 2 (1800mg, 2.72mmol) is added in the ethanol water of 20mL potassium hydroxide, 80 DEG C of oil is placed in
Flow back in bath 24h.Reaction is finished, and is cooled to room temperature, adds excessive concentrated hydrochloric acid, makes solution in acidity.After 1h is stirred at room temperature, to
Substantial amounts of distilled water is added in mixed solution, there are a large amount of yellow solids to separate out, reduce pressure suction filtration, obtain yellow powder product and (produce eventually
Thing 3) 600mg, yield 83%, purity 97%.
Product structure is detected by nuclear-magnetism, mass spectrum, is as a result shown, the present invention prepared 2,5- dimercaptos-
3,6- difluoro terephthalic acid (TPA)s.
Embodiment 3
The synthesis step of intermediate 1：
(1) the single port circle that 2,3,5,6- tetrafluoro terephthalic acid (TPA) (1190mg, 5mmol) of raw material adds 100mL to dry is weighed
In the flask of bottom.
(2) measure methyl alcohol (anhydrous, 50mL) with graduated cylinder to be added in single necked round bottom flask.
(3) concentrated sulfuric acid (2mL) is added dropwise, under room temperature, stirs 10min.It is subsequently placed in backflow 24h in oil bath.Question response is complete
Afterwards, room temperature being cooled to, substantial amounts of distilled water being added in mixture, there are a large amount of solids to separate out, reduce pressure suction filtration, obtains white plates
Crystalline product (i.e. intermediate 1) 1237mg, yield 93%, purity 98%.
The synthesis step of intermediate 2：
(1) cesium carbonate (3258mg, 10mmol) is placed in the reaction eggplant bottle of 25mL dryings, under nitrogen protection using note
Emitter throws 3- mercaptopropionic acids -2- Octyl Nitrites (1.9mL, 8.3mmol) in reaction eggplant bottle into.
(2) by the DMA (anhydrous, 15mL) after bubbling 10min under a nitrogen, shifted by vacuum tube
In the reaction eggplant bottle dried to 25mL.
(3) last, under nitrogen protection, intermediate obtained above 1 (1064mg, 4mmol) is added to 25mL dryings
Reaction eggplant bottle in, open stirring 0.5～12h.
(4), after reacting completely, the organic layer that is obtained by extraction, by silica gel chromatography post separation are purified, and obtain colourless viscous liquid product
Thing (i.e. intermediate 2) 1882mg, yield 71%, purity 97%.
The synthesis step of end-product 3：
Intermediate 2 (1800mg, 2.72mmol) is added in the ethanol water of 24mL NaOH, 90 DEG C of oil is placed in
Flow back in bath 24h.Reaction is finished, and is cooled to room temperature, adds excessive concentrated hydrochloric acid, makes solution in acidity.After 1h is stirred at room temperature, to
Substantial amounts of distilled water is added in mixed solution, there are a large amount of yellow solids to separate out, reduce pressure suction filtration, obtain yellow powder product and (produce eventually
Thing 3) 658mg, yield 91%, purity 97%.
Product structure is detected by nuclear-magnetism, mass spectrum, is as a result shown, the present invention prepared 2,5- dimercaptos-
3,6- difluoro terephthalic acid (TPA)s.
From above-described embodiment, the present invention has prepared mercapto-functionalized aryl carboxylic acid, obtains higher yield
And purity.
The explanation of above example is only intended to help and understands the method for the present invention and its core concept.It should be pointed out that right
For those skilled in the art, under the premise without departing from the principles of the invention, the present invention can also be carried out
Some improvement and modification, these improvement and modification are also fallen in the protection domain of the claims in the present invention.
Claims (10)
1. a kind of preparation method of mercapto-functionalized aryl carboxylic acid, it is characterised in that comprise the following steps：
A) to 2, the carboxyl of 3,5,6- tetrafluoro terephthalic acid (TPA)s is protected, and obtains intermediate 1；
B intermediate 1 and sulfydryl acid esters are carried out substitution reaction under conditions of alkali metal salt presence), intermediate 2 is obtained；
C) intermediate 2 is hydrolyzed reaction, obtains mercapto-functionalized aryl carboxylic acid.
2. preparation method according to claim 1, it is characterised in that step A) it is specially：
2,3,5,6- tetrafluoro terephthalic acid (TPA)s under conditions of methyl alcohol with the concentrated sulfuric acid carry out esterification, obtain 2,3,5,6- tetra-
Fluorine terephthalic acid (TPA) methyl esters.
3. preparation method according to claim 2, it is characterised in that the temperature of the esterification is backflow, and the time is 1
～24h.
4. preparation method according to claim 1, it is characterised in that the sulfydryl acid esters be 3- sulfydryl hexanol capronates,
One kind in methyl thioglycolate, 3- mercaptopropionic acid -3- methoxy butyl esters, 2 mercaptopropionic acid propyl ester, 3- mercaptopropionic acid -2- b hexyls
Or it is multiple.
5. preparation method according to claim 1, it is characterised in that the alkali metal salt is potassium phosphate, sodium carbonate, acetic acid
One or more in sodium, cesium carbonate, potassium carbonate, potassium acetate.
6. preparation method according to claim 1, it is characterised in that the intermediate 1, sulfydryl acid esters and alkali metal salt
Mol ratio is 1：(0.5～10)：(1～20).
7. preparation method according to claim 1, it is characterised in that the solvent of the substitution reaction is tetrahydrofuran, different
Propyl alcohol, dimethyl sulfoxide, acetonitrile, N,N-dimethylformamide, 1,3- dimethyl-2-imidazolinones, Macrogol 600, N, N- bis-
One or more in methylacetamide.
8. preparation method according to claim 1, it is characterised in that the temperature of the substitution reaction is 0～80 DEG C, reaction
Time is 0.5～12h.
9. preparation method according to claim 1, it is characterised in that the substitution reaction is a substitution reaction, two replacements
Reaction, three substitution reactions or four substitution reactions.
10. preparation method according to claim 1, it is characterised in that the hydrolysis is carried out under strongly alkaline conditions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610913260.7A CN106496080B (en) | 2016-10-19 | 2016-10-19 | A kind of preparation method of mercapto-functionalized aryl carboxylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610913260.7A CN106496080B (en) | 2016-10-19 | 2016-10-19 | A kind of preparation method of mercapto-functionalized aryl carboxylic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106496080A true CN106496080A (en) | 2017-03-15 |
| CN106496080B CN106496080B (en) | 2019-01-15 |
Family
ID=58317948
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610913260.7A Expired - Fee Related CN106496080B (en) | 2016-10-19 | 2016-10-19 | A kind of preparation method of mercapto-functionalized aryl carboxylic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106496080B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109096498A (en) * | 2018-08-27 | 2018-12-28 | 广东工业大学 | A kind of New Two Dimensional conductive metal organic framework material and preparation method thereof |
| CN115974729A (en) * | 2023-01-16 | 2023-04-18 | 营口昌成新材料科技有限公司 | Preparation method of 2- (2,2-difluoroethoxy) -6-trifluoromethylbenzenesulfonyl chloride |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104447452A (en) * | 2014-11-06 | 2015-03-25 | 广东工业大学 | Synthetic method of mercapto functionalized polyaryl carboxylic acid compound |
| CN104892656A (en) * | 2015-06-16 | 2015-09-09 | 广东工业大学 | Metal-organic framework material and synthetic method thereof |
| CN105531268A (en) * | 2013-05-07 | 2016-04-27 | 加拉佩格斯股份有限公司 | Novel compounds and pharmaceutical compositions thereof for the treatment of cystic fibrosis |
-
2016
- 2016-10-19 CN CN201610913260.7A patent/CN106496080B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105531268A (en) * | 2013-05-07 | 2016-04-27 | 加拉佩格斯股份有限公司 | Novel compounds and pharmaceutical compositions thereof for the treatment of cystic fibrosis |
| CN104447452A (en) * | 2014-11-06 | 2015-03-25 | 广东工业大学 | Synthetic method of mercapto functionalized polyaryl carboxylic acid compound |
| CN104892656A (en) * | 2015-06-16 | 2015-09-09 | 广东工业大学 | Metal-organic framework material and synthetic method thereof |
Non-Patent Citations (2)
| Title |
|---|
| JEAN-MICHEL BECHT 等: "Facile Introduction of SH Group on Aromatic Substrates via Electrophilic Substitution Reactions", 《J.ORG.CHEM.》 * |
| PIERRE-THOMAS SKOWRON 等: "On-Demand Cyclophanes: Substituent-Directed Self-Assembling,Folding, and Binding", 《JOURNAL OF ORGANIC CHEMISTRY》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109096498A (en) * | 2018-08-27 | 2018-12-28 | 广东工业大学 | A kind of New Two Dimensional conductive metal organic framework material and preparation method thereof |
| CN115974729A (en) * | 2023-01-16 | 2023-04-18 | 营口昌成新材料科技有限公司 | Preparation method of 2- (2,2-difluoroethoxy) -6-trifluoromethylbenzenesulfonyl chloride |
| CN115974729B (en) * | 2023-01-16 | 2024-02-02 | 营口昌成新材料科技有限公司 | Preparation method of 2- (2, 2-difluoroethoxy) -6-trifluoromethyl benzenesulfonyl chloride |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106496080B (en) | 2019-01-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105254589B (en) | A method of preparing heart failure drugs intermediate | |
| CN104177388B (en) | A kind of bridging bisamide base ytterbium and its preparation method and application | |
| CN105153110A (en) | Synthesis method for chiral intermediate of atorvastatin calcium | |
| CN106496080A (en) | A kind of preparation method of mercapto-functionalized aryl carboxylic acid | |
| CN103739500A (en) | Method for synthesizing and refining cinacalcet hydrochlorid | |
| CN104768955B (en) | The improved method being acylated for maytansinol | |
| CN103694153B (en) | The method of styracin and arylsulfinate Reactive Synthesis alkenyl sulfone compound | |
| CN105481623A (en) | Synthetic technology of hydroxyethylaniline ester (III) | |
| CN102911054B (en) | Preparation method of 4,4,4-trifluoro-2-butenoate | |
| CN106083539B (en) | A kind of synthetic method of list fluorine methoxyl group or the deuterated methoxy base class compound of single fluorine | |
| CN107056792A (en) | A kind of novel porphyrin class compound and its preparation method and application | |
| CN104761442B (en) | The preparation method of 1 (cyclohexenyl group of 2,6,6 trimethyl 3) 1,3 diacetyl | |
| CN103351376B (en) | Synthetic method of 2-thiophene ethylamine | |
| CN101327450B (en) | Aminoacid ion liquid carried Salen metallic catalyst and preparation method | |
| CN107337626A (en) | A kind of alkyl hydrosulfide functionalization aromatic carboxylic acids and preparation method thereof | |
| CN105175297B (en) | Synthesis and application of 4-formyl benzoic acid adamantine ester condensed o-aminobenzene thiophenol schiff base nickel complex | |
| CN103664631A (en) | Preparation method of naftifine hydrochloride | |
| CN102391170B (en) | A kind of preparation method of N, N-diallyl-5-methoxytryptamine hydrochlorides | |
| CN102875399B (en) | D-valine preparation method | |
| CN104774166A (en) | Synthetic method for disulfide diisopropyl xanthate | |
| CN109956854A (en) | A kind of preparation method of 7- methoxyl group -3- phenyl -1,2- dihydronaphthalene | |
| CN104230785B (en) | The synthetic method of 3-((4-chlorphenyl) sulfo-) the bromo-1-hydrogen-indole of-5- | |
| CN113024506B (en) | Process for preparing 3-formyltetrahydrothiopyran compounds | |
| CN103848854B (en) | The synthetic method of a kind of cupric bromide reagent and its preparation method, α-amido Propiophenone and derivative thereof | |
| CN107021488A (en) | Method for producing metal carbonate and catalyst used in the production method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190115 Termination date: 20211019 |